Apparatus and method for generating chemical signatures using differential desorption

ABSTRACT

The present invention is directed to a method and device to generate a chemical signature for a mixture of analytes. The present invention involves using a SPME surface to one or both absorb and adsorb the mixture of analytes. In an embodiment of the invention, the surface is then exposed to different temperature ionizing species chosen with appropriate spatial resolution to desorb a chemical signature for the mixture of analytes.

PRIORITY CLAIM

This application claims priority to (1) U.S. utility application Ser.No. 15/149,161 entitled “APPARATUS AND METHOD FOR RAPID CHEMICALANALYSIS USING DIFFERENTIAL DESORPTION”, inventor Brian D. Musselman,filed May 8, 2016, which claims priority to (2) U.S. utility applicationSer. No. 14/738,899 entitled “APPARATUS AND METHOD FOR RAPID CHEMICALANALYSIS USING DIFFERENTIAL DESORPTION”, inventor Brian D. Musselman,filed Jun. 14, 2015, which issued as U.S. Pat. No. 9,337,007 on May 10,2016, which claims priority to (3) U.S. Provisional Patent ApplicationNo. 62/012,417 entitled “ENSURING CONTACT TRANSFER FOR CRITICAL CHEMICALANALYSIS”, inventor Brian D. Musselman, filed Jun. 15, 2014; and (3)U.S. Provisional Patent Application No. 62/024,880 entitled “ENSURINGCONTACT TRANSFER FOR CRITICAL CHEMICAL ANALYSIS”, inventor Brian D.Musselman, filed Jul. 15, 2014, the contents of each of which areincorporated herein by reference in their entireties.

FIELD OF THE INVENTION

The present invention relates to methods and devices for measuring thatthe contact between an object and a collector has been sufficient formeasurement of chemical residues to be transferred to that collectorfrom the object that has previously been exposed to the chemical inorder to permit analysis of the chemical.

BACKGROUND OF THE INVENTION

Dr. Edmond Locard (13 Dec. 1877-4 May 1966) formulated Locard'sprinciple which states that the perpetrator of a crime will bringsomething into the crime scene and leave with something from it, andthat both can be used as forensic evidence. That is there is a contacttransfer between the perpetrator and the crime scene. This contacttransfer is the basis for much of Forensic Science. In many cases whatthe perpetrator brings and leaves is their fingerprint, morespecifically a representation that is made up of chemicals from theperpetrator's body. The visual record of a fingerprint is frequentlyused by forensic chemists to identify individuals who might have beenpresent at a crime scene.

SUMMARY OF THE INVENTION

In an embodiment of the invention, a Direct Analysis Real Time (DART)thermal profile measurement of a sample collected onto a sorbent fiberis analyzed using desorption gas heated to a plurality of differenttemperatures in positive ion mode. In an alternative embodiment of theinvention, a DART thermal profile measurement of a sample collected ontoa sorbent fiber is analyzed using desorption gas heated to a pluralityof different temperatures in negative ion mode. In various embodimentsof the invention, a DART thermal profile measurement of a sample thathas been in contact with a single sorbent fiber can be collected byusing desorption gas heated to a plurality of different temperatures.Either positive ion or negative ion or both ion mode mass spectra can becollected from the sorbent fiber in order to permit detection of a widerrange of chemicals should they be present.

In an embodiment of the invention a mesh fabricated from sorbent coatedwire replaces the sorbent fiber for sampling. The mesh can be made froma conductive material and can carry an electrical current. In anembodiment of the invention a sample can be deposited directly onto themesh. A current can be applied to the mesh in order to heat the wire.Sample related molecules can be desorbed from or in close proximity tothe mesh. The desorbed molecules can interact with the ionizing gas inthe region between the mesh and the atmospheric pressure ionization(API)-inlet of a spectrometer. The ions that are formed from thisinteraction can enter the spectrometer for analysis.

BRIEF DESCRIPTION OF THE DRAWINGS

This invention is described with respect to specific embodimentsthereof. Additional aspects can be appreciated from the Figures inwhich:

FIG. 1 depicts a schematic of a pressure sensor used to ensure thatintimate contact has been made by determining the duration of contactbetween the finger of a subject (135) and the collector using a circuitcapable of flowing current flow when the wire mesh (110) is depressedwith sufficient force to complete a connection through which electronscan flow between multiple sensor components (115) the circuit wires(120, 125) and a measuring device (130), according to an embodiment ofthe invention;

FIG. 2 depicts a schematic of a temperature sensor used to ensure thatintimate contact has been made between the wire mesh (110) and thesubject (not shown) by measuring the temperature of the wire mesh ormeasuring the change in temperature of a sensor surface (240) to which athermocouple (250) may be attached with electrodes or wires (245)connecting the thermocouple to its controller (235) as the wire mesh(110) is pushed down to contact that sensor surface;

FIG. 3 depicts a schematic of an circuit containing a conductivitysensor (352) used to ensure that intimate contact has been made bymeasuring the conductivity change through the circuit connected to thewire mesh (110) by using wires (120, 125) where the circuit is completedwhen the wire mesh is depressed by pressing the sample (135) against thewire mesh (110) so that it touches both sensor components (115) closingthe circuit which contains the sensor (352) to which a voltage may ormay not be applied by using a power supply (354). The change inconductivity being used in order to determine the duration of contact,according to an embodiment of the invention;

FIG. 4(A) depicts a schematic of an pressure sensor (460) used to ensurethat intimate contact has been made by measuring the pressure under thewire mesh (110) screen or the change in the air pressure under the wiremesh after it is depressed against the inlet opening (456) of a volume(462) to which a pressure generator (458) is attached to produce anincrease in pressure as the opening of the volume is covered by thesample (not shown) in order to determine the duration of contact,according to an embodiment of the invention;

FIG. 4(B) depicts a schematic of a finger (135) as the subject coveringboth the wire mesh (110) and opening of the volume (462) of the deviceshown in FIG. 4(A) as the finger is pressed against the wire meshblocking flow of gas into the volume (462) below the wire mesh. The lowpressure vacuum pump (458) is utilized to reduce the pressure in theenclosed volume. The vacuum in the volume is measured by the sensor(460) according to an embodiment of the invention;

FIG. 5(A) shows a drawing of a short solid phase micro extraction (SPME)fiber (566), attached to a conventional pipette tip holder (564) topermit manipulation of the fiber according to an embodiment of theinvention;

FIG. 5(B) shows a drawing of an elongated SPME fiber (568), attached toa conventional pipette tip holder (564) to permit manipulation of thefiber according to an embodiment of the invention;

FIG. 6(A) shows a prior art syringe aligned with the septum of a vial;

FIG. 6(B) shows the prior art syringe of FIG. 6(A) inserted into theseptum of a vial;

FIG. 6(C) shows a prior art GC injector being loaded with the syringe ofFIG. 6A;

FIG. 7 depicts a schematic of a SPME fiber (568) mounted on a robotpositioner (783) capable of moving the fiber in and out of the ionizingvolume located between the gas exit (786) of the ionizing source (784)and the inlet to the sensor (787), according to an embodiment of theinvention;

FIG. 8 depicts a schematic of two SPME fibers (566) attached toconventional pipette tip holders (564) inserted into a sample carrier(888) where each SPME fiber is separated by approximately 3 mm so thatthe fibers can be positioned in the ionization region between the gasexit (786) of the ionizing source (784) and the inlet (787) of thespectrometer (889), according to an embodiment of the invention;

FIG. 9(A) depicts a mass spectrum generated by desorption ionization ofan SPME fiber with a different sorbent coating to the SPME fibermeasured in FIG. 9(B) and separated by approximately nine (9) mm fromthe different sorbent coating to the SPME fiber measured in FIG. 9(B) inthe ‘Closeness Test for Matrix Effects’, according to an embodiment ofthe invention;

FIG. 9(B) depicts a mass spectrum generated by desorption ionization ofan SPME fiber with a different sorbent coating to the SPME fibermeasured in FIG. 9(A) and separated by approximately nine (9) mm fromthe different sorbent coating to the SPME fiber measured in FIG. 9(A) inthe ‘Closeness Test for Matrix Effects’, according to an embodiment ofthe invention;

FIG. 9(C) depicts a mass spectrum generated by desorption ionization ofan SPME fiber with a different sorbent coating to the SPME fibermeasured in FIG. 9(D) and separated by approximately one (1) mm from thedifferent sorbent coating to the SPME fiber measured in FIG. 9(D) in the‘Closeness Test for Matrix Effects’, according to an embodiment of theinvention;

FIG. 9(D) depicts a mass spectrum generated by desorption ionization ofan SPME fiber with a different sorbent coating to the SPME fibermeasured in FIG. 9(C) and separated by approximately one (1) mm from thedifferent sorbent coating to the SPME fiber measured in FIG. 9(C) in the‘Closeness Test for Matrix Effects’, according to an embodiment of theinvention;

FIG. 10(A) depicts the mass chromatogram for the ion detected at m/z 166ionized from a series of SPME fibers having a mixture of C18 and StrongCation Exchange sorbents coating positioned at decreasing distances fromone another during desorption ionization in the ‘Closeness Test forMatrix Effects’, according to an embodiment of the invention;

FIG. 10(B) depicts the mass chromatogram for the ion detected at m/z 144ionized from a series of multiple SPME fibers having a single sorbentC18 coating positioned at decreasing distances from one another duringdesorption ionization in the ‘Closeness Test for Matrix Effects’,according to an embodiment of the invention;

FIG. 11(A) depicts the total ion chromatogram (A) for ions of differentmass values generated by exposure of a single SPME fiber withPDMS-divinyl benzene coating to ionizing gas heated to a series ofincreasing temperature values corresponding to those temperaturesdepicted on the bottom axis, according to an embodiment of theinvention;

FIG. 11(B) depicts the mass chromatogram for the 443 Dalton (Da) ionsgenerated by exposure of a single SPME fiber with PDMS-divinyl benzenecoating to ionizing gas heated to a series of increasing temperaturevalues corresponding to those temperatures depicted on the bottom axis,according to an embodiment of the invention;

FIG. 11(C) depicts the mass chromatogram for the 325 Da ions generatedby exposure of a single SPME fiber with PDMS-divinyl benzene coating toionizing gas heated to a series of increasing temperature valuescorresponding to those temperatures depicted on the bottom axis,according to an embodiment of the invention;

FIG. 11(D) depicts the mass chromatogram for the 223 Da ions generatedby exposure of a single SPME fiber with PDMS-divinyl benzene coating toionizing gas heated to a series of increasing temperature valuescorresponding to those temperatures depicted on the bottom axis,according to an embodiment of the invention;

FIG. 12(A) shows the mass spectra generated during exposure of thePDMS-divinyl benzene SPME probe to approximately 100° C., according toan embodiment of the invention;

FIG. 12(B) shows the mass spectra generated during exposure of thePDMS-divinyl benzene SPME probe to approximately 250° C., according toan embodiment of the invention;

FIG. 12(C) shows the mass spectra generated during exposure of thePDMS-divinyl benzene SPME probe to approximately 300° C., according toan embodiment of the invention;

FIG. 13(A) shows multi-temperature SPME DART robotics MS analysis of afiber at an initial position where fiber is not exposed to ionizing gas,according to an embodiment of the invention;

FIG. 13(B) shows multi-temperature SPME DART robotics MS analysis of afiber at first exposure where first short segment of fiber is exposed toionizing gas, according to an embodiment of the invention;

FIG. 13(C) show multi-temperature SPME DART robotics MS analysis of afiber at second exposure where second short section adjacent to firstshort section of fiber is exposed to ionizing gas, according to anembodiment of the invention;

FIG. 13(D) show multi-temperature SPME DART robotics MS analysis of afiber at third exposure where third short section adjacent to secondshort section of fiber is exposed to ionizing gas, according to anembodiment of the invention;

FIG. 14(A) depicts the positioning of SPME fibers (566) mounted on arobotic sample positioner capable of positioning the individual fibersin the desorption ionization region between the gas exit (786) of theionizing source (785) and inlet of the spectrometer (787), according toan embodiment of the invention;

FIG. 14(B) depicts a view of the position of the SPME fibers mounted onthe robot module relative to the entrance of the spectroscopy system(787) with the ionizing source removed for visualization, according toan embodiment of the invention;

FIG. 15 shows a schematic of a robotic module (1592) holding pieces ofsorbent coated wire (1594) for analysis, according to an embodiment ofthe invention;

FIG. 16 depicts a schematic of a SPME fiber (566) mounted in a samplerneedle assembly (1696) which was held so that the fiber was insertedinto the ionization region between the gas exit (786) of the ionizingsource (784) and inlet (787) of the spectrometer (889), according to anembodiment of the invention;

FIG. 17 depicts a schematic of a fiber held by a digitally operatedmodule (783) designed to hold either the short SPME fiber (566) or theelongated SPME fiber (568) in-line with the ionization region betweenthe gas exit (786) of the ionizing source (784) and inlet (787) of thespectrometer, according to an embodiment of the invention;

FIG. 18(A)(i) shows the mass chromatogram generated for m/z 123 duringthe desorption ionization from an elongated PDMS-divinyl benzene SPMEprobe after utilizing thin layer chromatography (TLC) experimentalconditions to separate three components in a TLC test mixture from oneanother;

FIG. 18(A)(ii) shows the mass chromatogram generated for m/z 445 duringthe desorption ionization from an elongated PDMS-divinyl benzene SPMEprobe after utilizing thin layer chromatography (TLC) experimentalconditions to separate three components in a TLC test mixture from oneanother;

FIG. 18(A)(iii) shows the mass chromatogram generated for m/z 143 duringthe desorption ionization from an elongated PDMS-divinyl benzene SPMEprobe after utilizing thin layer chromatography (TLC) experimentalconditions to separate three components in a TLC test mixture from oneanother;

FIG. 18(B)(i) shows the mass spectrum from the analysis of the elongatedPDMS-divinyl benzene SPME probe after TLC separation of three componentsin TLC test mixture, where the spectrum shown was acquired at desorptiontimes of approximately 1.75 minutes and direct desorption ionizationfrom the fiber surface was complete by using helium gas ionized andheated to approximately 250° C., according to an embodiment of theinvention;

FIG. 18(B)(ii) shows the mass spectrum from the analysis of theelongated PDMS-divinyl benzene SPME probe after TLC separation of threecomponents in TLC test mixture, where the spectrum shown was acquired atdesorption times of approximately 1.95 minutes and direct desorptionionization from the fiber surface was complete by using helium gasionized and heated to approximately 250° C., according to an embodimentof the invention;

FIG. 18(B)(iii) shows the mass spectrum from the analysis of theelongated PDMS-divinyl benzene SPME probe after TLC separation of threecomponents in TLC test mixture, where the spectrum shown was acquired atdesorption times of approximately 2.5 minutes and direct desorptionionization from the fiber surface was complete by using helium gasionized and heated to approximately 250° C., according to an embodimentof the invention;

FIG. 19(A) shows the desorption ionization mass spectrum of a samplecontaining a mixture of chemicals extracted from a liquid onto a SPMEfiber where the desorption gas temperature is 100° C., according to anembodiment of the invention;

FIG. 19(B) shows the desorption ionization mass spectrum of a samplecontaining a mixture of chemicals extracted from a liquid onto a SPMEfiber where the desorption gas temperature is 200° C., according to anembodiment of the invention;

FIG. 19(C) shows the desorption ionization mass spectrum of a samplecontaining a mixture of chemicals extracted from a liquid onto a SPMEfiber where the desorption gas temperature is 300° C., according to anembodiment of the invention;

FIG. 20(A) shows the mass chromatogram for the protonated molecule ofheroin (1909) where the relative abundance increases after scan number600 up until scan number 775 corresponding to a desorption ionizationgas temperature of 300° C. according to an embodiment of the invention;

FIG. 20(B) shows the mass chromatogram for the protonated molecule ofLSD (1907) where the relative abundance increases after scan number 600up until scan number 775 corresponding to a desorption ionization gastemperature of 300° C. according to an embodiment of the invention;

FIG. 20(C)(i) shows the mass chromatogram for the protonated molecule ofa pesticide, Cyanazine (1905), where the relative abundance increasesafter scan number 25 up to scan number 150 corresponding to a desorptionionization gas temperature of 100° C., according to an embodiment of theinvention;

FIG. 20(C)(ii) shows the mass chromatogram for the protonated moleculeof a pesticide, Cyanazine (1905), where the relative abundance increasesafter scan number 300 up until scan number 425 corresponding to adesorption ionization gas temperature of 200° C., according to anembodiment of the invention;

FIG. 20(C)(iii) shows the mass chromatogram for the protonated moleculeof a pesticide, Cyanazine (1905), where the relative abundance increasesafter scan number 625 up until scan number 770 corresponding to adesorption ionization gas temperature of 300° C., according to anembodiment of the invention; and

FIG. 21 shows a diagram of the SPME fiber assembly of FIG. 5 with threeareas on the fiber tip, according to an embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION Definitions

The transitional term “comprising” is synonymous with “including,”“containing,” or “characterized by,” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified in the claim, but does not exclude additionalcomponents or steps that are unrelated to the invention such asimpurities ordinarily associated with a composition.

The transitional phrase “consisting essentially of” limits the scope ofa claim to the specified materials or steps and those that do notmaterially affect the basic and novel characteristic(s) of the claimedinvention.

A vacuum of atmospheric pressure is 1 atmosphere=760 ton. Generally,‘approximately’ in this pressure range encompasses a range of pressuresfrom below 10¹ atmosphere=7.6×10³ ton to 10⁻¹ atmosphere=7.6×10¹ ton. Avacuum of below 10⁻³ ton would constitute a high vacuum. Generally,‘approximately’ in this pressure range encompasses a range of pressuresfrom below 5×10⁻³ ton to 5×10⁻⁶ ton. A vacuum of below 10⁻⁶ torr wouldconstitute a very high vacuum. Generally, ‘approximately’ in thispressure range encompasses a range of pressures from below 5×10⁻⁶ ton to5×10⁻⁹ torr. In the following, the phrase ‘high vacuum’ encompasses highvacuum and very high vacuum. The prime function of the gas ion separatoris to remove the carrier gas while increasing the efficiency of transferof neutral molecules including analyte molecules into the massspectrometer. When constructed from non-conducting material, the gas ionseparator can also be used to insulate or shield the high voltageapplied to the inlet of the mass spectrometer.

A filament means one or more of a loop of wire, a segment of wire, ametal ribbon, a metal strand or an un-insulated wire, animal string,paper, perforated paper, fiber, cloth, silica, fused silica, plastic,plastic foam, polymer, Teflon, polymer impregnated Teflon, cellulose andhydrophobic support material coated and impregnated filaments. In anembodiment of the invention, a filament has a diameter of approximately50 microns. In an alternative embodiment of the invention, a filamenthas a diameter of approximately 100 microns. In another alternativeembodiment of the invention, a filament has a diameter of approximately500 microns. In another embodiment of the invention, a filament has adiameter of approximately 2 mm. In measuring the diameter of a filament,approximately indicates plus or minus twenty (20) percent. In anembodiment of the invention, the length of the filament is approximately4 mm. In an embodiment of the invention, the length of the filament(566) in FIG. 5(A) is approximately 9 mm. In an embodiment of theinvention, the length of the filament (566) in FIG. 5(B) isapproximately 25 mm. In an embodiment of the invention, the length ofthe holder (564) in FIG. 5(B) is approximately 30 mm. In anotherembodiment of the invention, the length of the filament is approximately150 mm. In measuring the length of a filament or holder, approximatelyindicates plus or minus twenty (20) percent.

A metal comprises one or more elements consisting of lithium, beryllium,boron, carbon, nitrogen, oxygen, sodium, magnesium, aluminum, silicon,phosphorous, sulfur, potassium, calcium, scandium, titanium, vanadium,chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium,germanium, arsenic, selenium, rubidium, strontium, yttrium, zirconium,niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver,cadmium, indium, tin, antimony, tellurium, cesium, barium, lanthanum,cerium, praseodymium, neodymium, promethium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium,platinum, gold, mercury, thallium, lead, bismuth, polonium, francium andradium. Thus a metal includes for example, a nickel titanium alloy knownas nitinol or a chromium iron alloy used to make stainless steel.

A plastic comprises one or more of polystyrene, high impact polystyrene,polypropylene, polycarbonate, low density polyethylene, high densitypolyethylene, polypropylene, acrylonitrile butadiene styrene, polyphenylether alloyed with high impact polystyrene, expanded polystyrene,polyphenylene ether and polystyrene impregnated with pentane, a blend ofpolyphenylene ether and polystyrene impregnated with pentane orpolyethylene and polypropylene.

A polymer comprises a material synthesized from one or more reagentsselected from the group comprising of styrene, propylene, carbonate,ethylene, acrylonitrile, butadiene, vinyl chloride, vinyl fluoride,ethylene terephthalate, terephthalate, dimethyl terephthalate,bis-beta-terephthalate, naphthalene dicarboxylic acid, 4-hydroxybenzoicacid, 6-hyderoxynaphthalene-2-carboxylic acid, mono ethylene glycol (1,2ethanediol), cyclohexylene-dimethanol, 1,4-butanediol, 1,3-butanediol,polyester, cyclohexane dimethanol, terephthalic acid, isophthalic acid,methylamine, ethylamine, ethanolamine, dimethylamine, hexamthylaminediamine (hexane-1,6-diamine), pentamethylene diamine,methylethanolamine, trimethylamine, aziridine, piperidine,N-methylpiperideine, anhydrous formaldehyde, phenol, bisphenol A,cyclohexanone, trioxane, dioxolane, ethylene oxide, adipoyl chloride,adipic, adipic acid (hexanedioic acid), sebacic acid, glycolic acid,lactide, caprolactone, aminocaproic acid and or a blend of two or morematerials synthesized from the polymerization of these reagents.

A plastic foam is a polymer or plastic in which a gaseous bubble istrapped including polyurethane, expanded polystyrene, phenolic foam, XPSfoam and quantum foam.

A mesh means one or more of two or more connected filaments, two or moreconnected strings, foam, a grid, perforated paper, screens, paperscreens, plastic screens, fiber screens, cloth screens, polymer screens,silica screens, Teflon screens, polymer impregnated Teflon screens,cellulose screens and hydrophobic support material coated or impregnatedmesh. In various embodiments of the invention, a mesh includes one ormore of three or more connected filaments, three or more connectedstrings, mesh, foam, a grid, perforated paper, screens, plastic screens,fiber screens, cloth, and polymer screens. In an embodiment of theinvention, a mesh can have approximately 10 filaments per cm. In analternative embodiment of the invention, a mesh can have approximately100 filaments per cm. In designing the number of filaments per cm,approximately indicates plus or minus twenty (20) percent.

Deployed means attached, affixed, adhered, inserted, or otherwiseassociated. Thus a paper screen can be deployed on a card where thepaper for the screen and the paper for the card are of a unitaryconstruction. A card means a sample holder. A card can be made of one ormore of paper, cardboard, insulating materials, conductive materials,plastic, polymers, minerals and metals. A mesh can be inserted and heldin a card. A mesh can be clamped in a card. Alternatively, a metal meshcan be welded into a metal card. A reservoir is a vessel used to containone or more of a liquid, a gaseous or a solid sample.

A sorbent fiber means a solid surface which has been coated with a thinchemical film that is capable of retaining certain chemical entities byinteracting with them forming either a non-covalent or in some cases acovalent bond between the chemicals on the surface and the chemicals inthe surrounding environment. In practice the thin film is greater thanapproximately 10 microns and less than approximately 500 microns inthickness. In designing the thickness of the film, approximatelyindicates plus or minus twenty (20) percent.

A desorption ionization source includes DART, DESI, a MALDI source, a UVlaser, an IR laser, atmospheric pressure chemical ionization (APCI)spray, directed electrospray, electrospray, a dielectric barrierdischarge, and a flowing after-glow plasma source.

In the following description, various aspects of the present inventionwill be described. However, it will be apparent to those skilled in theart that the present invention can be practiced with only some or allaspects of the present invention. For purposes of explanation, specificnumbers, materials, and configurations are set forth in order to providea thorough understanding of the present invention. However, it will beapparent to one skilled in the art that the present invention can bepracticed without the specific details. In other instances, well-knownfeatures are omitted or simplified in order not to obscure the presentinvention.

Parts of the description will be presented in data processing terms,such as data, selection, retrieval, generation, and so forth, consistentwith the manner commonly employed by those skilled in the art to conveythe substance of their work to others skilled in the art. As is wellunderstood by those skilled in the art, these quantities (data,selection, retrieval, generation) take the form of electrical, magnetic,or optical signals capable of being stored, transferred, combined, andotherwise manipulated through electrical, optical, and/or biologicalcomponents of a processor and its subsystems.

Various operations will be described as multiple discrete steps in turn,in a manner that is most helpful in understanding the present invention;however, the order of description should not be construed as to implythat these operations are necessarily order dependent.

Various embodiments will be illustrated in terms of exemplary classesand/or objects in an object-oriented programming paradigm. It will beapparent to one skilled in the art that the present invention can bepracticed using any number of different classes/objects, not merelythose included here for illustrative purposes

The invention is illustrated by way of example and not by way oflimitation in the figures of the accompanying drawings in which likereferences indicate similar elements. It should be noted that referencesto ‘an’ or ‘one’ embodiment in this disclosure are not necessarily tothe same embodiment, and such references mean at least one.

The unique characteristics that define a fingerprint image are inreality chemicals excreted through the skin that have been visualized byusing dyes that interact with those chemicals. Due in part to thedifficulty of preparing samples, the actual chemicals in thefingerprints derived from objects that the suspect touched, ingested,took as a medication or was otherwise exposed to, are not generallyrecognized as being identifiers that the suspect was present at a crimescene. Those chemicals may include drug metabolites, narcotics,explosive residues and foodstuffs that the suspect has come into contactwith prior to the event of forensic interest.

In practice, everyday thousands of chemical analyses of human subjectsare carried out to determine compliance with a drug treatment program,presence/absence of an illegal drug or in the medical setting todiagnose a disease. The medical community also examines the metabolitespresent in young children for signs of inherited diseases on a routinebasis.

Sample collection is relatively straight forward. In the case of buccalor urine samples there is sufficient volume to conduct chemical analysisusing a variety of chemical analysis instruments. In contrast to buccal,or urine samples the collection of chemicals from fingerprints foranalysis not a routine matter. Although uncommon, there are reports inwhich the chemicals present in a fingerprint have been imaged usingambient ionization mass spectrometry. Indeed, the use of the DARTambient ionization method for detection of metabolites of drugs directlyfrom fingerprints on a glass surface was documented in the firstpublication describing the method.

Solid phase extraction methods facilitate rapid isolation of targetcompounds from common chemicals that together make up a sample ofinterest. Solid phase extraction technologies have evolved to the pointwhere a wide array of devices is available for an analytical chemist touse with different types of samples. For example, the development ofthin film solid phase extraction coatings bound to fibers, so calledsolid phase micro extraction (SPME), has enabled the detection of tracequantities of specific targeted molecules for determination ofenvironmental toxins in water, pesticides in foods and beverages, andmetabolites in urine and blood to name a few application. SPME materialscan be optimized for use with different target compounds by changing thechemical composition of the sorbent material. Traditionally SPME derivedsamples are analyzed by using instrumentation including gaschromatography (GC), GC/mass spectrometry (MS) (GCMS), liquidchromatography (LC) and LCMS.

GC, GCMS, LC and LCMS instruments are capable of sampling a single fiberone at a time. Development of devices for desorption ionization ofmolecules direct from solids, and liquids in open air using a DARTsource has previously been described in U.S. Pat. No. 6,949,741“Atmospheric Pressure Ionization Source” which is herein expresslyincorporated by reference in its entirety. DART uses a heated carriergas to effect desorption of sample into that same carrier gas where gasphase ionization occurs. A gas ion separator described in U.S. Pat. No.7,700,913, “Sampling system for use with surface ionizationspectroscopy” which is herein expressly incorporated by reference in itsentirety can be used to improve the efficiency of sampling with DART.The DART method enabled direct desorption of SPME in different formatssuch as screens in open air which has led to new methods of analysis.FIG. 15 shows a schematic of sorbent coated screens (1594) mounted inthe groove (1593) of a robotic sample presentation module (1592) foranalysis, according to an embodiment of the invention.

In security applications chemical residues are sampled from the hand,fingers, clothing, suitcase surfaces and other locations by using clothswabs or plastic tickets. Sampling is carried out by a person followinga protocol that in most cases involves using a wand device that permitscollection of the sample without the person collecting the sample havingto touch the cloth or plastic ticket being used to sample the subject.The inspector is trained to ensure that a proper sample has beenacquired by applying sufficient force to the wand so that it makesintimate contact with the subject or surface being tested as called forin the sampling protocol. In an embodiment of the invention a wire meshcollector is used as a fingerprint collector. The surface of the wiremesh is coated with sorbent or sorbents capable of retaining chemicalsapplied to it. The force between the object being sampled and the wiremesh or other sampling device must be sufficient to ensure transfer ofthe chemical signature, which will be described as ‘intimate contact’.

In an embodiment of the invention in order to ensure that intimatecontact has been made a sensor is used to determine the duration ofcontact between the subject and the collector by using a circuit that iscapable of having current flow through the circuit when the wire mesh isdepressed with sufficient force to complete the circuit as shown inFIG. 1. In an alternative embodiment of the invention in order to ensurethat intimate contact has been made a sensor may measure the temperatureof the wire mesh or measure the change in temperature of the wire meshin order to determine the duration of contact as shown in FIG. 2. Thesensor surface (240) temperature is determined by converting the signalfrom the thermocouple (250) in contact with the sensor surface (240)where current flowing through components (245 and 235) results in anelectrical current determined by the measurement device (235). Thedevice described is use in order to determine the duration of contact,according to an embodiment of the invention. In another alternativeembodiment of the invention, in order to ensure that intimate contacthas been made a sensor may measure the conductivity of the wire mesh orchanges in the conductivity through the wire mesh in order to determinethe duration of contact, as shown in FIG. 3. In a further alternativeembodiment of the invention, in order to ensure that intimate contacthas been made a sensor may measure the air pressure under the wire meshscreen or change in the air pressure under the wire mesh in order todetermine the duration of contact. In another embodiment of theinvention in order to ensure that intimate contact has been made asensor may measure the vacuum in a chamber under the wire mesh screen orchange in the vacuum in a chamber under the wire mesh in order todetermine the duration of contact, as shown in FIG. 4. In an embodimentof the invention, the sensor output is connected to a device thatprovides a signal indicating that the duration and force of the contacthas been sufficient for completion of sample collection.

Exposure to dangerous chemical by breathing or by contact can thereforelead to some of those materials appearing in the fingerprint mixed withthe lipids that exit the skin. The identity of those materials might bedetermined with a viable sampling method and the proper detectionsystem.

DART analysis of fingerprint chemicals from surfaces has been reportingusing the DART ambient ionization method. Subsequently other ambientionization methods have been utilized including desorption electrosprayionization which was used to permit detection of individual specks of agunshot residue dispersed throughout the fingerprint of an individualreported to have fired a weapon shortly before acquisition of the data.DART has been used to detect drug and drug metabolites from aprescription drug taken orally. Practically speaking the detection ofexplosives and other chemicals using ion mobility spectrometry is commonpractice in airport and other secure settings. This is also a form ofchemical fingerprint detection.

In an embodiment of the invention direct sampling of the chemicalspresent on the surface of a finger has been accomplished by first havingthe subject make contact with a sorbent coated surface. The surface wassubsequently analyzed in seconds by using an ambient ionization directanalysis in real time (DART) mass spectrometry device without extractionof the surface that had been touched by the finger. Ions detected in themass spectrum are used to determine that the individual from which thesample was acquired had come into contact with those chemicals in therecent past or had come into contact with another individual who hadbeen exposed to that chemical.

The desorption ionization region is located between the DART source exitand the atmospheric pressure inlet of the detection system.

There remain encumbrances to the employment of the DART technique for avariety of samples and various experimental conditions. A schematicrepresentation of two different SPME fibers is shown in FIG. 5. In orderto permit manipulation of the fiber by either hand or robotic means thefiber is mounted to a holder, in this case a plastic pipette tip (564)which has been heated and compressed to surround and bind the proximalend of the fiber. FIG. 5(A) shows a drawing of a short solid phase microextraction (SPME) fiber (566), the proximal end of which is molded intothe distal end of a plastic pipette tip (564) according to an embodimentof the invention. FIG. 5(B) shows a drawing of an elongated SPME fiber(568), also molded into the distal end of a plastic pipette tip,according to an embodiment of the invention. With SPME the capture andretention of compounds of interest is carried out by the chemicalspresent in the sorbent coating binding to the fiber surface. The sorbentof each fiber is capable of binding chemicals based on the functionalgroups that are present in the molecule while excluding binding ofmolecules that do not have the functional groups that the sorbent canbind. Extraction occurs when the fiber comes into contact with either agas or liquid containing those molecules with appropriate functionalgroups and thereby affinity to be chemically bound to the sorbent.Sampling can be made either from a sample constrained by an enclosure ordirectly from the surrounding environment. These easy-to-use samplingmethods have facilitated development of numerous devices suitable forsampling chemicals in the field.

When sampling liquids using SPME, the first step of the analysis is toimmerse the sorbent coated fiber into the liquid. The analysis can beimproved by either moving the fiber itself or the container holding thesample and the fiber. This movement facilitates interaction between thechemicals in the sample and the sorbent on the fiber. The criticalsecond step of the analytical process is the transfer of compoundstrapped on the sorbent coated fiber to an instrument for the analysis tooccur. This step typically involves inserting the fiber into a singleenclosed region to effect thermal desorption of the target compoundsinto the gas phase for gas chromatography (GC) or GC/MS analysis. Asshown in FIG. 6(A)-FIG. 6(C) for the headspace GC experiment the syringe(672) used to collect a quantity of gas in the headspace (674) above aliquid sample (689) has a hollow needle (684) connected to the syringe.The needle is inserted into the headspace volume (674) by pushing thesyringe down so that the needle passes through a flexible septum (643)which is pierces. The septum acts to maintain separation between theoutside atmosphere and the headspace. A heater block (676) is often usedto increase the temperature of the sample vial so that volatilemolecules from the sample (689) into the headspace. The headspace sampleis drawn into the volume of the syringe (672) by pulling on the syringeplunger (670) as shown in FIG. 6B. In FIG. 6A the plunger in depressedbefore the syringe is pushed through a septum (643) into the headspaceregion (674) of the sample vial (693). In FIG. 6B the plunger inwithdrawn and a portion of the headspace gas drawn up into the syringe(672). The syringe (672) containing the headspace sample is withdrawnfrom the sample vial by pulling the syringe away from the vial thusremoving the needle from the sample vial. In the GC experiment theheadspace sample is transferred from the syringe volume into a heatedregion identified as the injection port (680) as depicted in FIG. 6C byfirst inserting the needle of the syringe (684) through a flexibleseptum (645) and then depressing the syringe plunger (670) to expel thegas. Inside the heated injector port a glass liner (678) is used toisolate that the headspace gases from the metal of the heater and thisinert liner is designed to minimize retention of chemicals for anylength of time. In the gas chromatography instruments the injectorvolume (678) is maintained at a high temperature in order to efficientlyvaporize the compounds from the sorbent coated fiber. Once vaporized thesample exits the injector as the force of flowing gas under highpressure pushes the chemicals through a pressurized fitting (681) intothe gas chromatography column (682) which permits separation of two ormore of the individual chemicals in the sample from one another. Afterthe individual chemicals spend time in the separation device they exitit and are transferred into the detector for analysis.

In an alternative application the sorbent coated fiber can be insertedinto a sample injector loop typically fashioned from a small length ofnarrow bore capillary tubing in order to complete introduction of aliquid chromatography (LC) or LC/MS system for analysis.

In order to complete the introduction of sorbent coated fiber intoeither the heated, pressurized GC injector, or the loop of a LC systemthe SPME fiber is protected from interaction with the injector bypositioning it inside a needle (672). The rigid needle is used topuncture the flexible septum (680) which is used to seal this injectorhole so that chemicals desorbed from the SPME fiber can only exit theinjector by moving into the chromatographic injector volume. Thereforekeeping the pressure inside the injector while the needle encasing theSPME fiber is introduced into the injector volume and until the sampleis desorbed from that fiber and directed onto the separation column iscritical to the prior art. Once the needle has penetrated through theseptum the SPME fiber is pushed out of the needle into the open volumeof the injector where the heat effects rapid desorption of all chemicalspreviously bound by the sorbent. The requirement for a syringe needle tobe rigid and not bend when being pushed into and through the septumresults in the diameter of that metal tube being between approximately0.2 mm to approximately 0.5 mm. The SPME fiber in prior art thereforedoes exceed the inside diameter of the syringe. The most popular Solidphase micro extraction (SPME) fibers are commercially available as apolyimide fiber, approximately 300 micron in diameter, with a singletype of sorbent materials bound to the surface.

The development of open air ionization systems such as DART anddesorption electrospray ionization (DESI) have enabled the directdesorption and detection of chemicals bound to the sorbent fibers. Thesemethods eliminate the sample injector requirement from the experiment.In prior art experiments plasma-based ambient ionization includingAtmospheric pressure chemical ionization, direct analysis in real time,and dielectric barrier discharge mediated ionization have been utilizedfor ionization of compounds directly from different types of sorbentmaterials used for solid phase extraction in bulk form instead of thinfilms. In those experiments the liquid containing a sample was drawninto the sorbent material encased in a syringe and allowed to incubatefor a limited amount of time. A series of solvent washes and changes ofsolvent permit removal of salts and non-targeted sample relatedchemicals from the bulk material present in the sample of analyticalinterest. In the DART experiment the temperature of the ionizing gas canbe varied using at least one of two methods. Firstly, a heaterincorporated into the source can be used to heat the carrier gas.Secondly, the sample molecules can be applied to a mesh and the meshheated. In an embodiment of the present invention the carrier gas isheated for the experiment. In practice varying the desorption gastemperature permits a more complete thermal desorption of the sample byenabling analysis of the same sample at multiple temperatures thusproviding for ionization of a wider range of compounds of interest inthat sample. In an embodiment of the experiment, DART-based desorptionionization from the SPME device can be used to either completelyvaporize the chemicals on the fiber or complete a slower distillation ofthose same chemicals by first operating at a lower temperature and thenchanging to a higher temperature. This thermal desorption occurs inclose proximity to the atmospheric pressure inlet (API) of an LC/MS orLC/MS/MS. In some experiments the SPME fibers are presented to theionizing gas by using either a manual introduction system as shown inFIG. 7 or a robotic sample positioner as depicted in FIG. 8. In FIG. 7,the SPME fiber (568) is moved into the desorption ionization regionbetween the heated gas exit (786) of the ionizing source (784) bypushing the holder (783) along a guide. Ions formed by desorption fromthe fiber enter the inlet tube (787) of the spectrometer for analysis.

The use of the ambient ionization systems decreases the time requiredfor analysis of each SPME fiber thus reducing the time required forsample analysis and in many cases sample preparation requirements. Asits utility of the SPME method has grown the types of sorbents availablehave increased. Unfortunately, the use of one sorbent per fiber peranalysis has been the dominant method because of the requirement thatthe sample be introduced into a narrow injector port. That is theprevious rule of use was that one SPME fiber was used per experiment ineither GC, LC, GC/MS or LC/MS. Commercial vendors of the SPME fibersdeveloped mixed-mode fibers in order to facilitate collection of a widerrange of chemical functional groups on a single fiber. These fibers havetwo or more different sorbents on their surface. Initial DART-MSexperiments using these mixed-mode SPME fibers to collect two differenttypes of chemicals present in samples yielded poor data consistent withthe presence of only a single compound. That is, a significantdiscrimination against some chemicals extracted by the second sorbentwas observed. It was hypothesized that the chemicals extracted by thedifferent sorbents were interacting with the ionizing gas and thosechemicals with high proton affinities were scavenging the availableprotons in the ionizing gas resulting in only those high proton affinitymolecules being detected in the DART-mass spectrum. This competitiveionization condition has previously been called the “matrix effect” inliquid chromatography/mass spectrometry.

The use of more than one sorbent as a means to collect a wider range ofchemical entities for chemical characterization of a sample is desirablebecause it can result in the collection of a wider variety of chemicalentities which, once analyzed, will generate a more comprehensive listof the chemicals present in the original sample. Combining theinformation from two or more different analyses of the same materialresults in the development of a chemical signature for that material. Inorder to examine the optimum positioning required to reduce or eliminatematrix effects between fibers relative to one a series of desorptionionization experiments were completed using four different fiberholders, similar in design to the 3 mm spacing fiber holder (888) shownin FIG. 8. The other holders were produced with spacing between samplesof approximately 9 mm, approximately 2 mm and approximately 1 mm. Thevarious fiber holders provided a means to reliably position the fibersion the ionization region between the gas exit (786) of the ionizationsource (784) and the inlet (787) of the spectroscopy system (889) wereused for a series of experiments some of which are described below.

Experiment 1

A solution containing glucose and the drug benzocaine was extractedusing a first multi-sorbent coated SPME fiber and a secondsingle-sorbent coated SPME fiber. The first fiber had both C-18 and acation exchange sorbents, while the second fiber had a C-18 sorbent.Thus the first SPME fiber can extract a wider range of chemicals withdifferent physical properties than the second SPME fiber. The first andsecond fiber were sequentially presented into the desorption ionizationregion passing through it at a constant rate of speed in an embodimentof the invention. Depending on the holder used the fibers were separatedby: approximately 9 mm, approximately 3 mm, approximately 2 mm orapproximately 1 mm, where approximately in this range means plus orminus ten (10) percent. The mass spectrum generated by desorptionionization of the two different fibers separated by approximately 9 mmof space are shown in FIG. 9(A) and FIG. 9(B). Unexpectedly, the majorions produced by glucose are detected at m/z 180 (936), and m/z 197(938) and the major ion for benzocaine is detected at m/z 166 (934). Themass spectra are clearly different although the glucose related ions 936and 938 are present in both data. In subsequent experiments, as theindividual fibers were positioned closer to each other during ionizationthe relative abundance of the protonated benzocaine detected at m/z 166decreases until at 1 mm separation it is no longer detectable.Unexpectedly, as the separation decreases the mass spectra become nearlyidentical as shown in FIG. 9(C) and FIG. 9(D) where benzocaine is notdetected and the glucose related ions are very abundant. At the time ofcarrying out these experiments, it was not known or expected that thespectra from different surfaces separated by 1 mm can be effected by thepresence of the other surface in a desorption ionization experiment. Inan embodiment of the invention, as the separation between the fibers wasdecreased below approximately 1 mm the resulting data can no longer bedifferentiated from one another by using the desorption ionization massspectrum. As a result, the capability to detect the active drugcomponent in a sample can be compromised if the fibers are analyzed intoo close proximity to each other. Mass chromatograms plot the relativeabundance of the different ions as a function of fiber separation duringdesorption ionization, as shown in FIG. 10. The relative abundance ofthe protonated benzocaine at m/z 166, which is only extracted from thesolution by the first fiber, is shown in the top panel FIG. 10 (A).Initially, with the 9 mm spacing between fibers, the protonatedbenzocaine at m/z 166 ion abundance (see FIG. 10(A) mass chromatogram)is significant as the first fiber, the fiber having which has a mixedmode sorbent composition, enters the ionization region at 0.3 minutesand then disappears at 0.4 minutes until the second fiber, the singlesorbent fiber that does not retain the benzocaine, enters the ionizationregion at 0.5 minutes. The glucose related ion at m/z 180 ion abundance(see FIG. 10(B) mass chromatogram) is detected at a consistent relativeabundance regardless of fiber separation during the ionizationexperiment. Results from the analysis of the second fiber set, separatedby only 3 mm, are presented in the second box. The first fiber of thatset enters the ionization region at 1.25 minutes and the relativeabundance of the protonated benzocaine m/z 166 ion decreases by morethan half relative to the 9 mm separation result. The generation ofprotonated benzocaine continues to decrease by another factor of 2 whenthe third set of fibers, separated by only 2 mm, enter the ionizationregion at time 2.0 minutes. Finally, at the fibers separated by only 1mm enter the ionization region at 2.7 mm the protonated benzocaine isbarely detected In an embodiment of the invention SPME fiber placementmust be sufficient to reduce or eliminate the simultaneous desorption ofanalyte from adjacent fibers in order to facilitate independentionization of all molecules retained by each of the fibers in order toreduce or eliminate matrix effects.

In an alternative embodiment of the invention, multiple fibers withmixed sorbents were analyzed at different positions with a minimumspacing required in order to isolate the fibers from each other. Aperson of ordinary skill in the art would understand that the spacingcan be determined by factors selected from the group consisting of theionization affinity of the components in the sample, the vapor pressureof the components in the sample the heat of enthalpy of the componentsin the sample, the entropy of the components in the sample and otherfactors affecting the gas phase volatility of the components in thesample. Analysis with a spacing of between approximately 1 mm andapproximately 10 mm can present obvious starting points for determiningthe required spacing. In various embodiments of the invention, thespacing between fibers can be reduced to as little as approximately 0.1mm as by using different desorption ionization sources having smallerionization region requirements. Those sources include, but are notlimited to, atmospheric pressure chemical ionization, laser desorption,and desorption electrospray ionization which have capability fordesorption ionization from areas of as little as approximately 100micron. In another embodiment of the invention, multiple fibers withdifferent sorbents were simultaneously analyzed at different positionsby using multiple ionizers. In another alternative embodiment of theinvention, multiple fibers with different sorbent type SPME fiberscontacted with mixed sorbents were simultaneously analyzed at differentpositions. Independent desorption can result in ionization of thedifferent molecules from the sample.

Experiment 2

In LC/MS analysis the matrix effect is often eliminated by utilizingchromatography to separate the molecules from each other prior to theirarrival in the ionizing region of the instrument. The chromatographicmaterial permits separation of matrix components from the compounds ofinterest as those components bind to the chromatographic material for alonger time period than the matrix components thus physically resolvingone component from analysis at the same time as another component. Inthe desorption ionization experiment, rather than using a physicalseparation to remove the matrix compounds the thermal properties of thedifferent compounds in a sample including; matrix and compound ofinterest, are leveraged to permit detection of a more representativechemical signature for the sample. Analyzing the same sample by exposingit to the ionization gas at a series of increasing temperature valuesserves to reduce the matrix effect by removing the low temperaturevolatile matrix molecules prior to desorption of the larger, moreanalytically useful molecules, namely those that desorb at the highertemperatures. This experiment is referred to as thermal profiling of thesample. The thermal profile can be generated with samples desorbed fromeither inert or sorbent coated surfaces.

In practice exposure of the SPME fibers to the ionizing gas may involvemovement of the fiber into and out of the gas region several times. Inthis case a region of the fiber that has already been exposed to a lowtemperature ionizing gas will subsequently be exposed to the highertemperature gas along with the a previously unexposed section of thefiber in very close proximity.

In an embodiment of the invention, the same fiber can be analyzed atmultiple temperatures in order to (i) potentially reduce the matrixeffects that might be observed and (ii) enable a more rapid and costeffective analysis that requires only one fiber to desorb multiple typesof compounds in a single experiment. Results from the analysis of amixture of chemicals including: quinine, acetazolamide and rhodamine Bon a single SPME fiber after exposure at five different temperatures areshown in FIG. 11, where the total ion chromatogram FIG. 11(A), and ionchromatograms for three target chemicals protonated rhodamine B at m/z443 FIG. 11(B), protonated quinine at m/z 325 FIG. 11(C) and protonatedacetazolamide at m/z 223 FIG. 11(D), known to have different optimalthermal desorption temperatures, are displayed as a function of thedesorption ionization gas temperature. A PDMS-divinyl-benzene coatedSPME fiber was used for this experiment; however any fiber can be usedprovided it collected the material of interest. DART gas temperature wasapproximately 100° C. when a small section of the distal end of the SPMEprobe was inserted into the desorption ionization region from time zeroto one minute; the probe was then withdrawn from the region. The DARTgas temperature was raised to approximately 150° C., approximately 200°C., approximately 250° C., and approximately 300° C. with the probebeing reinserted further into the ionizing region at each increasingtemperature so that a previously unexposed section of the sorbent wassubject to interrogation using the hotter desorption ionization gas. Asin the first experiment sequence described above, the probe waswithdrawn from the region while the gas temperature was raised to eachnew temperature. Mass spectra generated during exposure of thePDMS-divinyl benzene fiber SPME probe to different desorptiontemperatures are shown in FIG. 12 at approximately 100° C. FIG. 12(A),approximately 250° C. FIG. 12(B) and approximately 300° C. FIG. 12(C).In FIG. 12(A) the component with the maximum relative abundance isAcetazolamide (peak 1201). In FIG. 12(B) both quinine (peak 1204) andrhodamine B (peak 1202) are detected while rhodamine B (peak 1202)dominates the mass spectrum acquired when the desorption gas temperatureis 300° C. FIG. 12(C) see peak 1202. The mass spectra demonstrate thatthe utility of the single fiber experiment as a means to thermallydesorb different materials for analysis at different times. A schematicof the desorption ionization region into which the single elongated SPMEfiber has been inserted to four different lengths in order to carry outthe multiple temperature, single fiber experiment, is shown in FIG. 13.In FIG. 13 a multi-temperature SPME DART robotics MS analysis of a fiberat an initial position where fiber is not exposed to ionizing gas isshown in FIG. 13(A), a first exposure where first short segment of fiberis exposed to ionizing gas is shown in FIG. 13(B), a second exposurewhere second short section adjacent to first short section of fiber isexposed to ionizing gas is shown in FIG. 13(C), and a third exposurewhere third short section adjacent to second short section of fiber isexposed to ionizing gas is shown in FIG. 13(D).

Experiment 3

In the prior art SPME-MS experiment a new fiber would be required foreach sample presented for analysis since desorption of all the chemicalentities on the entire fiber is completed at a single temperature in aninjector as shown in FIG. 6(C). By design, the injector of a GC or LCsystem can accommodate only one fiber thus limiting direct interrogationof the sample to one analysis. In an embodiment of the present SPME-DARTanalysis invention, the thermal profile experiment can be completedusing multiple fibers with a different fiber being analyzed at eachdesorption ionization temperature setting. SPME fibers are immersed in asolution so that the entire length of the sorbent coated surface wasimmersed in the volume of solution containing the sample, such thatretention of sample along the length of the SPME fiber is uniform.Following an appropriate extraction period the individual fiber isremoved from the sampling container. The series of SPME fibers (566)were mounted into the automated sampler comprised of a linear rail(1491), and SPME mounting module (1490) positioned such that the SPMEfiber sorbent surface passes between the ionizing source exit (786) andspectrometer entrance (787) are presented for analysis at measuredintervals so that, most critically, no two fibers can be positioned inthe desorption source (785) ionization region at the same time. A modelof the system is shown in FIGS. 14(A) and 14(B). In a typical SPME-basedsample by using desorption ionization for the analysis a single fiber issufficient for a single analysis, in an embodiment of the invention theexperiment is not completed until multiple fibers have been analyzed andthe combined information is integrated to describe all of the chemicalsdetected in the sample

In various embodiments of the invention, a desorption ionization thermalprofile measurement of a sample is completed using desorption gas heatedto a plurality of different temperatures with mass spectra collected inpositive ion and negative ion mode at each temperature. In an embodimentof the invention, a thermal profile measurement of a sample is analyzedusing desorption gas heated to three different temperatures. The ThermalProfile is formed by the collection of three positive ion and threenegative ion mass spectra. Alternately, as not all spectrometers havenegative ion detection capability a Thermal Profile may contain onlypositive ion mass spectra. Similarly, for some classes of compounds,only negative ions might be produced leading to a Thermal Profile thatcontains only negative ion mass spectra. The compiled data collected inall of these possible configurations form the thermal profile of thematerial. Predictably compounds that vaporize at lower temperature willappear in the low temperature mass spectra while the less volatilematerials will be detected at higher temperatures. Given a system withgood temperature control all of the SPME fibers (566) will be analyzedin a short time interval with the same temperature gas for each sampleprobe presented into the desorption ionization region FIG. 14.

In an embodiment of the invention three SPME fibers (FIG. 14(A) (566)were used to extract mixtures of pesticides and narcotics from a sampleof commercial synthetic urine which is known to contain several of themajor chemicals in urine and no narcotics or pesticides. In theexperiment the three fibers loaded with sample were pushed through theionization region where the desorption ionization gas was 100° C. forthe first 150 scans, then 200° C. from scan 295 to 425 and finally 300°C. from scans 630 to 750 where desorption of the targeted narcoticsoccurs. The same region of the fiber was exposed to the ionizing gas ateach temperature setting. The sample laden SPME fiber were positionedside-by-side in the SPME module (888) mounted on the motorized linearrail (1491) and the motorized rail was turned on and pushed the moduleresulting in the three SPME fibers entering the desorption ionizationregion between the source exit (786) and the and the spectrometerentrance (787) region. A desorption gas temperature of 100° C. was usedfor the initial experiment. Mass spectrum acquired from the first SPMEfiber is shown in FIG. 19(A). Species were observed at 1902 (m/z 214)and 1905 (m/z 242) representing the volatile pesticide molecules weredetected. The two pesticides, Cyanazine, and Desmetryn were detectedwith good sensitivity at both 100° C., 200° C. and 300° C. The increasein desorption gas temperature to 300° C. results in the ionization anddetection of the drugs which were also extracted from the sample by theSPME fiber. The mass chromatogram for the protonated pesticide Cyanazinem/z 242 is shown in the trace of FIG. 20(C)(i). The pesticides weredetected on all three SPME fibers in that first sample set. Thenarcotics, known to be present, were not detected so the desorption gastemperature was increased to 200° C. After the DART gas temperaturestabilized the SPME fibers were once again pushed through the desorptionionization region. In this case only the pesticides were detected onceagain as shown in the mass spectrum in FIG. 19(B). The mass chromatogramfor the protonated pesticide Cyanazine m/z 242 desorbed using 200° C.gas is shown in the trace of FIG. 20(C)(ii). Still seeking to detect thenarcotics the DART gas temperature was increased to 300°. Once the DARTgas temperature stabilized at the third, higher temperature, the SPMEfibers were again pushed through the desorption ionization region foranalysis. In an embodiment of the invention, the 300° C. gas wassufficient to permit desorption ionization of the low vapor pressuredrug compounds that were not detected at lower temperatures as well assome pesticide residues that remained on the fiber due to incompletedesorption at the lower gas temperatures. The mass spectrum in FIG.19(C) shows 1902 (m/z 214), 1905 (m/z 242), 1907 (m/z 324), 1909 (m/z373). These species represent the protonated molecule for heroin (1909),LSD (1907), Cyanazine (1905), and Desmetryn (1902). Operation at highertemperatures can be used to enhance the detection of those narcotics,despite the fact that their relative abundance when compared to thepesticide Cyanazine is low, the mass chromatograms for the protonatedmolecules of heroin and LSD are strong and steady as shown in FIG. 20(A)and FIG. 20(B). The mass chromatogram for the protonated pesticideCyanazine m/z 242 desorbed using 300° C. gas is shown in the trace ofFIG. 20(C)(iii). The use of sequential desorption at different gastemperatures thus has two benefits (1) it permits detection of differentmolecules at different temperatures and (2) it improves the sensitivityfor detecting chemicals in a mixture by reducing the abundance ofmolecules desorbed at any one time based on volatility.

FIG. 21 shows a SPME tip, where according to various embodiments of theinvention, the total length 2116 of the tip 568 can be divided up into aplurality of regions for analysis. In FIG. 21 the tip 568 is divided upinto three lengths 2113, 2114 and 2115. In an embodiment of theinvention, the three lengths 2113, 2114 and 2115 are equal. In anembodiment of the invention, the tip is 9 mm in length and 2113, 2114and 2115 are each 3 mm in length. In an alternative embodiment of theinvention, the three lengths 2113, 2114 and 2115 are not equal.

In an embodiment of the experiment a series of different sorbent coatedfibers are used to isolate targeted molecules from a sample. Each of thedifferent sorbent fibers is analyzed independently at the sametemperature or a thermal profile experiment can be completed for eachfiber.

In an embodiment of the invention, a screen fabricated from sorbentcoated wire replaces the sorbent fiber for sampling FIG. 15(A). Thesorbent coated screen has the advantage sampling from a greater surfacearea in the same time period as a single fiber. In an embodiment of theinvention, a large surface area screen can have different regions coatedwith different sorbents. The multi-sorbent screen can be exposed to thesame sample in the same container in order to complete the SPMEexperiment. Desorption ionization of different sections of the wire meshcan be completed using either the same or different temperatures. Thedifferent sections of the mesh can be separated by either application ofsorbent to different sections or by removing sections of the sorbentcoated wire.

In an embodiment of the experiment a piece of sorbent coated wire meshare positioned in a sample carrier FIG. 15(B). The carrier body (1592)permits positioning of the sample laden wire mesh in the desorptionionization region between the gas exit of the ionizing source and theinlet of the spectrometer. Multiple wire mesh from either differentsamples or the same sample can be analyzed by placing one piece of meshinto each slot (1594) and (1595) and pushing those wire mesh through thedesorption ionization region sequentially if desired.

In an embodiment of the invention a thermal desorption profile can begenerated by using a collection of wire mesh that have been exposed tothe same sample, placing one wire mesh in each of the even numberedslots (1594) of the carrier (1592). Analysis of the first sample iscompleted at the starting temperature after which the carrier is pushedalong its axis until the desorption ionization region is aligned withthe odd number slot (1595) which is empty. While positioned with theempty slot in the desorption ionization region the gas temperature canbe raised to the higher temperature necessary for the analysis of thesecond sample without consuming that sample. Once the temperaturereaches the second desired temperature the second wire mesh laden withsample is moved by the carrier to a position where it is in thedesorption ionization region. The process is repeated as desired tofully characterize the sample.

In an embodiment of the invention screens coated with different sorbentsthat have been exposed to the same sample can be mounted in the carrierand analyzed in order to generate more comprehensive results from theanalysis of that single sample.

In an embodiment of the invention the width and height of the wire meshcan be less than the total volume of the open space of each position(1595) in the carrier (1592).

In an embodiment of the experiment the sorbent fiber is a long fiber(FIG. 5(B)). The long fiber is utilized in order to enable multipleanalyses from the same fiber with different temperature DART gas. Theposition of the fiber can be adjusted manually FIG. 16 or by roboticmeans FIG. 17 between analyses so that different regions of the fibercan be exposed to the gas. The device shown in FIG. 5(B) has a fiber ofsufficient length so that the sorbent region in the desorptionionization region is unique for each temperature.

In an embodiment of the invention the sorbent coated mesh is fashionedinto a cylinder that wraps around a solid material such as a wire orfiber. The mesh can be present as an extension of the syringe plungerfor example.

Experiment 4

Thin layer chromatography (TLC), is commonly used to permit a visualseparation of chemicals contained in a sample from each other by using athin film of sorbent. Generally in TLC, the sorbent is an inorganicmaterial bound to the surface of a glass plate, metal plate or plasticsurface by physical and/or chemical forces. The TLC experiment isundertaken in a series of steps: (i) spotting of the sample to thesorbent coated surface a short distance from its proximal end, (ii)immersion of the proximal end into a tall container having a volume ofthe solvent that is less than sufficient to reach the spot of thesample, and (iii) allowing the solvent to be absorbed by the sorbent andthereby move the sample up the surface based on the chemical interactionof different components in the sample with the sorbent. Differentcomponents therefore are separated from each other based on theirstructure, solubility, binding characteristics as well as chemicalcomposition. In another embodiment of the present invention, thefunction of the SPME fiber or mesh is therefore similar to the functionof the thin layer inorganic materials bonded to glass plates or plasticsurfaces of thin layer chromatography (TLC) devices.

When conducting the multi-temperature SPME desorption ionizationexperiments it was noted that at the same desorption gas temperature thesame chemicals took longer to desorb from by the SPME fiber than fromthe typical glass tube. Desorption ionization off of a glass surface canoften results in a brief desorption event, that means desorption of thesample is complete in a short interval of time (e.g., less thanapproximately 10 seconds) provided the material being analyzed has asufficiently high vapor pressure and the desorption gas has a sufficientheat to complete vaporization ranging from room temperature to moderatetemperature (e.g., approximately 350° C.±25° C.). In this temperaturerange approximately means plus or minus ten (10) percent. In the case ofthe SPME fiber the sample ionization period was observed to be longerthan for the same compounds desorbed from glass surfaces. In some casesit was difficult to desorb chemicals completely even at elevatedtemperatures (e.g., approximately 350° C.±35° C.). In this temperaturerange approximately means plus or minus ten (10) percent. To investigatethe efficiency of different solvents for removal of chemicals a dyemixture was utilized as the sample, the proximal end of the SPME fiberwas dipped into a solvent for short periods of time and analyzed byvisual means as well as with DART-MS to detect the rate of removal ofthe chemical.

After only short exposure times the interval require for removal of dyewith strong solvents was observed to be uniform. However, given a longerperiod of time the removal of dye was observed to be less successful. Asthose sorbent coated regions had not been immersed in the solvent itseemed that the analyte had migrated up the sorbent coating into theuntreated region. When continuing the desorption ionization analysisalong the length of the fiber it was determined that some chemicals hadbeen pushed further along the fiber than others essentially presentingthe fiber as being capable of completing a TLC based separationexperiment.

Experiment 5

In an embodiment of the invention, an aliquot of sample was deposited ona small section of the surface of a SPME fiber (see FIG. 5(B)) andallowed to dry. The sample position was at a distance of approximately2-3 mm from the proximal end of the SPME fiber. The proximal end of thefiber with the sample laden portion was then inserted into a vesselcontaining a volume of solvent or solvents required for thechromatographic separation. The depth of the solvent was less thanapproximately sixty (60) percent of the distance between the proximalend of the fiber and the sample laden position on its surface. Theportion of the fiber containing the sample was not immersed in thesolvent. As in the conventional TLC experiment the vessel or chambercontaining the solvent and the sample laden fiber with its proximal endimmersed in the solvent is closed to permit the solvent vapor to rise inthe chamber. The interaction of solvent vapor, sample molecule andsorbent chemicals results in the transit of molecules from the proximalto the distal end of the SPME fiber by capillary action. As the solventfront reaches a point near to the distal end of the SPME fiber it isremoved from the vessel to stop the separation. Direct analysis of thefiber with DART-MS was undertaken either manually by hand (FIG. 16) orby using fiber holder (FIG. 17) to push the SPME fiber through thedesorption ionization region at a steady rate. The results of analysisof a SPME Fiber after TLC separation of three components in a standardTLC test mixture are shown in FIG. 18(A). Direct desorption ionizationfrom the fiber surface as a function of position was completed usinghelium gas ionized and heated to approximately 250° C. The fiber waspushed through the ionization region at rate of speed of approximately0.2 mm/second, according to an embodiment of the invention; the largearrow at the top of the figure identifies the point at which the sorbentcoated fiber enters the ionization region, the arrow at approximately1.75 minutes indicates the point of application of the sample where someof those molecules in the sample are not soluble in the solvent and thusdo not move, the arrow at approximately 1.95 minutes shows the movementof molecules that are soluble and thus move with the solvent up thefiber and the arrow at approximately 2.5 minutes shows the movement of amolecules that migrates with the solvent but are not well resolved fromeach other as they may be different isomers which may or may not havedifferent metal atoms in their structure. Mass chromatograms show therelative abundance of ions for three different chemicals m/z 123 seeFIG. 18(A)(i), m/z 445 see FIG. 18(A)(ii), and m/z 143 see FIG.18(A)(iii). Ionization was completed by using desorption ionization withhelium gas at 250° C. Fiber speed of presentations was 0.2 mm/second.The mass spectra for each of the major ions are shown in FIG. 18(B)where the mass spectra shown in FIG. 18(B)(i) was acquired for materialswhich did not move from the starting point at 1.75 minutes, where themass spectra shown FIG. 18B(ii) is for the material present on the fiberhaving migrated 1.2 mm up the fiber and where the mass spectra shownFIG. 18B(iii) is for the material present on the fiber having migrated12 mm up the fiber.

In an embodiment of the invention the SPME fiber can be coated with avariety of sorbents including but not limited to C-18,PDMS/divinyl-benzene, PDMS, C-8, C-4 and other materials commonly usedfor SPME analysis. In an embodiment of the invention an untreated silicacoated fiber can be utilized. In an embodiment of the invention thefiber can be coated with carbon, functionalized carbon, tenax orinorganic materials. In an embodiment of the invention PDMS coatedfibers can be used.

In an embodiment of the invention the proximal end of the SPME fiber isimmersed in an aliquot of sample in order to extract the chemicalspresent in that sample as in the conventional SPME operation. The SPMEfiber is removed from the sample containing solution. The sample ladenSPME fiber is then inserted into a vessel containing a small volume ofan appropriate solvent or solvents in order to remove a portion of thesample from its proximal end in order to leave a short length of sampleof the fiber for separation by using the SPME-fiber for the TLCanalysis. The volume of solvent in the vessel being no deeper than theshort distance from the proximal end of the fiber but less than enoughto remove the entire sample. Some portion of the fiber containing thesample must not be immersed in the solvent as it might remove thesample. As in the conventional TLC experiment the sample laden SPMEfiber is placed in a second vessel to permit the solvent to transit fromthe proximal to the distal end of the SPME fiber. Separations of thecomponents of the sample are made by interaction of those chemicals withsolvents and/or the sorbent on the SPME fiber. As the solvent frontreaches a point near to the distal end of the SPME fiber the fiber isremoved from the vessel to stop the separation. Direct analysis of thefiber can be undertaken with DART-MS. In an embodiment of the inventionthe SPME fiber can be coated with a variety of sorbents including butnot limited to C-18, PDMS/divinyl-benzene, PDMS, C-8, C-4 and othermaterials commonly used for SPME analysis. In an embodiment of theinvention an untreated silica coated fiber can be utilized. In anembodiment of the invention the fiber can be coated with carbon,functionalized carbon, tenax or inorganic materials. In an embodiment ofthe invention, the fiber can be PDMS coated.

In an embodiment of the invention a collection of SPME fibers can beaffixed to one another in order to increase the surface area availablefor the experiment. The fibers can be joined at the proximal or distalend or at some position along the fiber in order to create a bundle offibers.

In an embodiment of the invention, the sample laden SPME fiber can beinserted into a vessel or tube with the proximal end connected to avolume of solvent or solvents that are being continuously evaporated byuse of a heating source. The solvent vapor immerses the volume of theSPME fiber flowing in the direction from its proximal to distal end. Inan embodiment of the invention one or more SPME fiber can be positionedin the tube or vessel to permit simultaneous TLC. As in the conventionalTLC analysis separation of the constituents of the sample are made byinteraction of those chemicals with solvent or solvents and the sorbenton the SPME fiber. As the solvent front reaches a point near to thedistal end of the SPME fiber the fiber is removed from the vessel tostop the separation.

Experiment 7

In an embodiment of the present invention, chemicals collected by thesorbent can be bound by reversible interactions and can be released whenthe surface is wetted with solvents in which those chemicals aresoluble. For example, interactions between a polar solvent and moleculescan be disrupted using acetonitrile. Further, the solvent simultaneouslydesorbs most of the chemicals from the surface. In an embodiment of theinvention, a stream of ionized solvent is directed at the sample ladenSPME fiber to permit desorption ionization of chemicals bound to thesorbent fiber for detection. In order to permit desorption of differentchemicals from the same fiber the composition of the solvent beingemitted from the desorption ionization source is changed over the courseof movement of the fiber through the desorption ionization region.

A method of ionizing a sample comprising the steps of receiving aplurality of sorbent coated fibers, each of a length and a diameter topermit multiple exposure of the plurality of sorbent coated fibers,contacting at least one of the plurality of sorbent coated fibers with asample, separating the plurality of sorbent coated fibers by a distanceand directing a plurality of different temperatures of a carrier gasfrom one or more desorption ionization sources at a target area on theplurality of sorbent coated fiber to ionize molecules present on thetarget area.

A method of ionizing a sample comprising the steps of receiving aplurality of sorbent coated fibers, each of a length and a diameter topermit multiple exposure of the plurality of sorbent coated fibers,contacting at least one of the plurality of sorbent coated fibers with asample, separating the plurality of sorbent coated fibers by a distanceand directing a plurality of different temperatures of a carrier gasfrom one or more desorption ionization sources at a target area on theplurality of sorbent coated fiber to ionize molecules present on thetarget area, further comprising the steps of analyzing molecules with amass spectrometer in one or both positive and negative ionization modes.

A kit for analyzing a plurality of sorbent coated fibers comprising aplurality of sorbent coated fibers with an average length and an averagediameter to permit multiple exposure of the plurality of sorbent coatedfibers to a plurality of different temperature gasses from a desorptionionization source, a holder for positioning the plurality of sorbentcoated fibers such that the plurality of sorbent coated fibers areseparated at least by a distance, where the holder or other meansenables contact between the plurality of sorbent coated fibers and oneor more samples and a means to adjust a position of one or both theholder and the plurality of sorbent coated fibers such that a pluralityof different temperatures of a carrier gas from a desorption ionizationsource are directed at one or more target areas on the plurality ofsorbent coated fibers.

A kit for analyzing a plurality of sorbent coated fibers comprising aplurality of sorbent coated fibers with an average length and an averagediameter to permit multiple exposure of the plurality of sorbent coatedfibers to a plurality of different temperature gasses from a desorptionionization source, a holder for positioning the plurality of sorbentcoated fibers such that the plurality of sorbent coated fibers areseparated at least by a distance, where the holder or other meansenables contact between the plurality of sorbent coated fibers and oneor more samples and a means to adjust a position of one or both theholder and the plurality of sorbent coated fibers such that a pluralityof different temperatures of a carrier gas from a desorption ionizationsource are directed at one or more target areas on the plurality ofsorbent coated fibers, where the distance is between a lower limit ofapproximately 1 mm and an upper limit of approximately 10 mm.

A kit for analyzing a plurality of sorbent coated fibers comprising aplurality of sorbent coated fibers with an average length and an averagediameter to permit multiple exposure of the plurality of sorbent coatedfibers to a plurality of different temperature gasses from a desorptionionization source, a holder for positioning the plurality of sorbentcoated fibers such that the plurality of sorbent coated fibers areseparated at least by a distance, where the holder or other meansenables contact between the plurality of sorbent coated fibers and oneor more samples and a means to adjust a position of one or both theholder and the plurality of sorbent coated fibers such that a pluralityof different temperatures of a carrier gas from a desorption ionizationsource are directed at one or more target areas on the plurality ofsorbent coated fibers, where the distance is between a lower limit ofapproximately 1 mm and an upper limit of approximately 10 mm, where theaverage length is between a lower limit of approximately 4 mm and anupper limit of approximately 150 mm.

A kit for analyzing a plurality of sorbent coated fibers comprising aplurality of sorbent coated fibers with an average length and an averagediameter to permit multiple exposure of the plurality of sorbent coatedfibers to a plurality of different temperature gasses from a desorptionionization source, a holder for positioning the plurality of sorbentcoated fibers such that the plurality of sorbent coated fibers areseparated at least by a distance, where the holder or other meansenables contact between the plurality of sorbent coated fibers and oneor more samples and a means to adjust a position of one or both theholder and the plurality of sorbent coated fibers such that a pluralityof different temperatures of a carrier gas from a desorption ionizationsource are directed at one or more target areas on the plurality ofsorbent coated fibers, where the distance is between a lower limit ofapproximately 1 mm and an upper limit of approximately 10 mm, where theaverage length is between a lower limit of approximately 4 mm and anupper limit of approximately 150 mm, where the average diameter isbetween a lower limit of approximately 0.05 mm and an upper limit ofapproximately 2 mm.

A kit for analyzing a plurality of sorbent coated fibers comprising aplurality of sorbent coated fibers with an average length and an averagediameter to permit multiple exposure of the plurality of sorbent coatedfibers to a plurality of different temperature gasses from a desorptionionization source, a holder for positioning the plurality of sorbentcoated fibers such that the plurality of sorbent coated fibers areseparated at least by a distance, where the holder or other meansenables contact between the plurality of sorbent coated fibers and oneor more samples and a means to adjust a position of one or both theholder and the plurality of sorbent coated fibers such that a pluralityof different temperatures of a carrier gas from a desorption ionizationsource are directed at one or more target areas on the plurality ofsorbent coated fibers, where the distance is between a lower limit ofapproximately 1 mm and an upper limit of approximately 10 mm, where theaverage length is between a lower limit of approximately 4 mm and anupper limit of approximately 150 mm, where the average diameter isbetween a lower limit of approximately 0.05 mm and an upper limit ofapproximately 2 mm, where one or more of the plurality of sorbent coatedfibers is made up of one or more materials selected from the groupconsisting of C-18, PDMS/divinyl-benzene, PDMS, C-8 and C-4.

A kit for analyzing a sorbent coated fiber comprising a sorbent coatedfiber of a length and a diameter to permit multiple exposure of thesorbent coated fiber to a plurality of different temperature gasses froma desorption ionization source, a reagent fiber containing reactivechemicals, and a holder for positioning the sorbent coated fiber at adistance from the reagent fiber, where the holder is adapted to positionone or both the sorbent coated fiber and the reagent fiber to direct aplurality of different temperatures of a carrier gas from a desorptionionization source at a target area on one or both the sorbent coatedfiber and the reagent fiber to analyze molecules present on the one orboth the sorbent coated fiber and the reagent fiber.

A kit for analyzing a sorbent coated fiber comprising a sorbent coatedfiber of a length and a diameter to permit multiple exposure of thesorbent coated fiber to a plurality of different temperature gasses froma desorption ionization source, a reagent fiber containing reactivechemicals, and a holder for positioning the sorbent coated fiber at adistance from the reagent fiber, where the holder is adapted to positionone or both the sorbent coated fiber and the reagent fiber to direct aplurality of different temperatures of a carrier gas from a desorptionionization source at a target area on one or both the sorbent coatedfiber and the reagent fiber to analyze molecules present on the one orboth the sorbent coated fiber and the reagent fiber, where the distanceis between a lower limit of approximately 1 mm and an upper limit ofapproximately 10 mm.

A kit for analyzing a sorbent coated fiber comprising a sorbent coatedfiber of a length and a diameter to permit multiple exposure of thesorbent coated fiber to a plurality of different temperature gasses froma desorption ionization source, a reagent fiber containing reactivechemicals, and a holder for positioning the sorbent coated fiber at adistance from the reagent fiber, where the holder is adapted to positionone or both the sorbent coated fiber and the reagent fiber to direct aplurality of different temperatures of a carrier gas from a desorptionionization source at a target area on one or both the sorbent coatedfiber and the reagent fiber to analyze molecules present on the one orboth the sorbent coated fiber and the reagent fiber, where the distanceis between a lower limit of approximately 1 mm and an upper limit ofapproximately 10 mm, where the length is between a lower limit ofapproximately 4 mm and an upper limit of approximately 150 mm.

A kit for analyzing a sorbent coated fiber comprising a sorbent coatedfiber of a length and a diameter to permit multiple exposure of thesorbent coated fiber to a plurality of different temperature gasses froma desorption ionization source, a reagent fiber containing reactivechemicals, and a holder for positioning the sorbent coated fiber at adistance from the reagent fiber, where the holder is adapted to positionone or both the sorbent coated fiber and the reagent fiber to direct aplurality of different temperatures of a carrier gas from a desorptionionization source at a target area on one or both the sorbent coatedfiber and the reagent fiber to analyze molecules present on the one orboth the sorbent coated fiber and the reagent fiber, where the distanceis between a lower limit of approximately 1 mm and an upper limit ofapproximately 10 mm, where the length is between a lower limit ofapproximately 4 mm and an upper limit of approximately 150 mm, where thediameter is between a lower limit of approximately 0.05 mm and an upperlimit of approximately 2 mm.

A method of ionizing a sample on a sorbent coated fiber comprising thesteps of receiving a sorbent coated fiber of a length and a diameter topermit multiple exposure of the sorbent coated fiber, contacting thesorbent coated fiber with the sample, directing a first carrier gas witha first temperature from a desorption ionization source at a firsttarget area on the sorbent coated fiber to generate a plurality of firstsample ions, and directing a second carrier gas with a secondtemperature at a second target area on the sorbent coated fiber togenerate a plurality of second sample ions directing one or both theplurality of first sample ions and the plurality of second sample ionsinto an analysis instrument.

A method of analyzing a sorbent coated fiber comprising the steps ofreceiving a sorbent coated fiber of a length and a diameter to permitmultiple exposure of the sorbent coated fiber to a plurality ofdifferent temperature gasses from a desorption ionization source,bringing the sorbent coated fiber into contact with a sample, directinga carrier gas with a first temperature from the desorption ionizationsource at a first target area on the sorbent coated fiber to generate aplurality of first sample ions, directing a carrier gas with a secondtemperature from the desorption ionization source at a second targetarea on the sorbent coated fiber to generate a plurality of secondsample ions, directing one or both the plurality of first sample ionsand the plurality of second sample ions into an analysis instrument andanalyzing one or both the plurality of first sample ions and theplurality of second sample ions.

While the systems, methods, and devices have been illustrated bydescribing examples, and while the examples have been described inconsiderable detail, it is not the intention of the applicants torestrict or in any way limit the scope of the appended claims to suchdetail. It is, of course, not possible to describe every conceivablecombination of components or methodologies for purposes of describingthe systems, methods, and devices provided herein. Additional advantagesand modifications will readily be apparent to those skilled in the art.Therefore, the invention, in its broader aspects, is not limited to thespecific details, the representative system, method or device, andillustrative examples shown and described. Accordingly, departures maybe made from such details without departing from the spirit or scope ofthe applicant's general inventive concept. Thus, this application isintended to embrace alterations, modifications, and variations that fallwithin the scope of the appended claims. Furthermore, the precedingdescription is not meant to limit the scope of the invention. Rather,the scope of the invention is to be determined by the appended claimsand their equivalents.

What is claimed is:
 1. A device comprising: a desorption ionizationsource adapted to generate a first stream of energetic particles at afirst temperature and a second stream of energetic particles at a secondtemperature, where the desorption ionization source is adapted to directthe first stream of energetic particles towards a target area on thesorbent coated fiber, where the sorbent coated fiber has a length and adiameter, where the sorbent coated fiber has been in contact with asample, where the first stream of energetic particles forms a pluralityof first sample ions, where the desorption ionization source is adaptedto direct the second stream of energetic particles towards the targetarea on the sorbent coated fiber, where the second stream of energeticparticles forms a plurality of second sample ions; and an analyzer,adapted to analyze one or both one or more of the plurality of firstsample ions and one or more of the plurality of second sample ions. 2.The device of claim 1, where the length of the sorbent coated fiber isbetween: a lower limit of approximately 4 mm; and an upper limit ofapproximately 150 mm.
 3. The device of claim 1, where the diameter ofthe sorbent coated fiber is between: a lower limit of approximately 0.05mm; and an upper limit of approximately 2 mm.
 4. The device of claim 1,further comprising a holder adapted to hold the sorbent coated fiberwhile one or both the first stream of energetic particles and the secondstream of energetic particles impacts the sorbent coated fiber.
 5. Thedevice of claim 1, where the desorption ionization source is anelectrospray ionization source.
 6. The device of claim 1, where thedesorption ionization source is a DART ionization source.
 7. The deviceof claim 1, where the desorption ionization source utilizes a stream ofcarrier gas molecules to direct one or both the first energeticparticles and the second energetic particles at the target area.
 8. Thedevice of claim 7, where the carrier gas is selected from the groupconsisting of helium, nitrogen, oxygen, neon, argon, krypton, and xenon.9. The device of claim 7, where the temperature of the stream of carriergas molecules is between: a lower limit of approximately 270° K; and anupper limit of approximately 600° K.
 10. The device of claim 1, wherethe step of analyzing comprises analyzing molecule ions with a massspectrometer in one or both positive and negative ionization modes. 11.A device comprising: a desorption ionization source adapted to generatea plurality of first sample ions and a plurality of second sample ions,where the plurality of first sample ions are formed from a first streamof energetic particles with a first temperature impacted a sorbentcoated fiber and the plurality of second sample ions are formed from asecond stream of energetic particles with a second temperature impactedthe sorbent coated fiber; and an analyzer, adapted to analyze one ormore of the plurality of first sample ions and the plurality of secondsample ions.
 12. The device of claim 11, where the sorbent coated fiberhas a length between: a lower limit of approximately 4 mm; and an upperlimit of approximately 150 mm.
 13. The device of claim 11, where thesorbent coated fiber has a diameter between: a lower limit ofapproximately 0.05 mm; and an upper limit of approximately 2 mm.
 14. Thedevice of claim 11, further comprising a holder adapted to hold thesorbent coated fiber while one or both the first stream of energeticparticles and the second stream of energetic particles impacts thesorbent coated fiber.
 15. The device of claim 11, where the desorptionionization source is selected from the group consisting of DART, DESI,MALDI, UV laser, IR laser, APCI, directed electrospray, electrospray,dielectric barrier discharge, and flowing after-glow plasma.
 16. Thedevice of claim 11, where the desorption ionization source utilizes astream of carrier gas molecules to direct one or both the firstenergetic particles and the second energetic particles at the sorbentcoated fiber.
 17. The device of claim 16, where the carrier gas isselected from the group consisting of helium, nitrogen, oxygen, neon,argon, krypton, and xenon.
 18. The device of claim 16, where thetemperature of the stream of carrier gas molecules is between: a lowerlimit of approximately 270° K; and an upper limit of approximately 600°K.
 19. A device comprising: a first desorption ionization source adaptedto generate a plurality of first sample ions formed from a first streamof energetic particles with a first temperature impacting a sorbentcoated fiber; a second desorption ionization source adapted to generatea plurality of second sample ions formed from a second stream ofenergetic particles with a second temperature impacting the sorbentcoated fiber; and an analyzer, adapted to analyze one or more of theplurality of first sample ions and the plurality of second sample ions.20. The device of claim 19, where one or both the first desorptionionization source and the second desorption ionization source areselected from the group consisting of DART, DESI, MALDI, UV laser, IRlaser, APCI, directed electrospray, electrospray, dielectric barrierdischarge, and flowing after-glow plasma.